PMID- 25639733
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20150520
LR  - 20150211
IS  - 1463-9084 (Electronic)
IS  - 1463-9076 (Linking)
VI  - 17
IP  - 8
DP  - 2015 Feb 28
TI  - Insights into hydrogen bond donor promoted fixation of carbon dioxide with 
      epoxides catalyzed by ionic liquids.
PG  - 5959-65
LID - 10.1039/c4cp05464d [doi]
AB  - Catalytic coupling of carbon dioxide with epoxides to obtain cyclic carbonates is 
      an important reaction that has been receiving renewed interest. In this 
      contribution, the cycloaddition reaction in the presence of various hydrogen bond 
      donors (HBDs) catalyzed by hydroxyl/carboxyl task-specific ionic liquids (ILs) is 
      studied in detail. It was found that the activity of ILs could be significantly 
      enhanced in the presence of ethylene glycol (EG), and EG/HEBimBr were the most 
      efficient catalysts for the CO2 cycloaddition to propylene oxide. Moreover, the 
      binary catalysts were also efficiently versatile for the CO2 cycloaddition to 
      less active epoxides such as styrene oxide and cyclohexene oxide. Besides, the 
      minimum energy paths for this hydrogen bond-promoted catalytic reaction were 
      calculated using the density functional theory (DFT) method. The DFT results 
      suggested that the ring-closing reaction was the rate-determining step in the 
      HEBimBr-catalyzed cycloaddition reaction but the EG addition could remarkably 
      reduce its energy barrier as the formation of a hydrogen bond between EG and the 
      oxygen atom of epoxides led this process along the standard SN2 mechanism. As a 
      result, the ring-opening reaction became the rate-determining step in the 
      EG/HEBimBr-catalyzed cycloaddition reaction. The work reported herein helped the 
      understanding and design of catalysts for efficient fixation of CO2 to epoxides 
      via hydrogen bond activation.
FAU - Liu, Mengshuai
AU  - Liu M
AD  - The Academy of Fundamental and Interdisciplinary Science, Harbin Institute of 
      Technology, Harbin 150080, PR China. shengli@hit.edu.cn sunjm@hit.edu.cn.
FAU - Gao, Kunqi
AU  - Gao K
FAU - Liang, Lin
AU  - Liang L
FAU - Wang, Fangxiao
AU  - Wang F
FAU - Shi, Lei
AU  - Shi L
FAU - Sheng, Li
AU  - Sheng L
FAU - Sun, Jianmin
AU  - Sun J
LA  - eng
PT  - Journal Article
PL  - England
TA  - Phys Chem Chem Phys
JT  - Physical chemistry chemical physics : PCCP
JID - 100888160
EDAT- 2015/02/03 06:00
MHDA- 2015/02/03 06:01
CRDT- 2015/02/03 06:00
PHST- 2015/02/03 06:00 [entrez]
PHST- 2015/02/03 06:00 [pubmed]
PHST- 2015/02/03 06:01 [medline]
AID - 10.1039/c4cp05464d [doi]
PST - ppublish
SO  - Phys Chem Chem Phys. 2015 Feb 28;17(8):5959-65. doi: 10.1039/c4cp05464d.